Exothermic cosmetic

ABSTRACT

A PACKAGED SELF-HEATING COSMETIC, SUCH AS A SHAVING CREAM, INCLUDES SEPARATE EXOTHERMICALLY REACTIVE SULFINIC ACID OR SULFINATE REDUCTANT AND AN OXIDANT, WHICH CONVERTS THE REDUCTANT TO THE CORRESPONDING SULFONIC ACID OR SULFONATE, WHICH SERVES AS A SURFACE-ACTIVE INGREDIENT OF THE HEATED COSMETIC. MEANS ARE PROVIDED FOR DISPENSING THE PACKAGED REDUCTANT AND OXIDANT AND MIXING THEM TOGETHER SO THAT THEY REACT AND HEAT SHAVING CREAM OR OTHER COSMETIC PRODUCT CONSTITUENTS WITH WHICH THE EXOTHERMIC REACTION MIXTURE IS BROUGHT INTO CONTACT. PREFERABLY, THE REDUCING AGENT EMPLOYED IS A METALLIC OR NON-METALLIC SALT OF BENZENE SULFINIC ACID OR ALKYL BENZENE SULFINIC ACID AND THE OXIDIZING AGENT IS AN AQUEOUS SOLUTION OF HYDROGEN PEROXIDE.

3,772,203 EXOTHERMIC COSMETIC Frederick William Gray, Summit, N.J.,assignor to Colgate-Palmolive Company, New York, N.Y. No Drawing.Continuation of application Ser. No.

848,335, Aug. 7, 1969. This application July 26,

1972, Ser. No. 275,381

Int. Cl. Clld 17/04 US. Cl. 252-90 14 Claims ABSTRACT OF THE DISCLOSUREA packaged self-heating cosmetic, such as a shaving cream, includesseparate exothermically reactive sulfinic acid or sulfinate reductantand an oxidant, which converts the reductant to the correspondingsulfonic acid or sulfonate, which serves as a surface-active ingredientof the heated cosmetic. Means are provided for dispensing the packagedreductant and oxidant and mixing them together so that they react andheat shaving cream or other cosmetic product constituents with which theexothermic reaction mixture is brought into contact. Preferably, thereducing agent employed is a metallic or non-metallic salt of benzenesulfinic acid or alkyl benzene sulfinic acid and the oxidizing agent isan aqueous solution of hydrogen peroxide.

This is a continuation of application Ser. No. 848,335, filed Aug. 7,1969.

Heated cosmetics have been known to the art and for certainapplications, as in shaving creams, they have been known to be moreeffective than cold products, especially in their ability to morerapidly soften the hairs of a beard and to prepare the beard for a closeshave In recent years pressurized shaving cream, dispensed fromso-called aerosol cans, have allowed the user to apply an alreadyprepared lather, thereby saving the time and effort which was previouslyneeded to work up a lather with shaving soap and brush. Such instantlathers have usually been dispensed at room temperature or at a slightlylower temperature, loss of heat content being due to vaporization orsome of the more volatile components of the lathers as the pressure ofthe composition is reduced to atmospheric. Attachments have been madefor pressurized dispensers so that the lather discharged therefrom willbe electrically or mechanically heated but most of these devices areunwieldy, ineificient and comparatively expensive. Thus, self-heatingcosmetic preparations, wherein the product dispensed from its containeris heated by chemical reaction, are desirable products and research hasbeen conducted in efforts to prepare commercially acceptable ones.

It has been known to dispense two fluids simultaneuosly from apressurized container and it has also been known that by reactingtogether an oxidant and a reductant, heat will often be generated. It isalso recognized that pressurized solutions of hydrogen peroxide willrelease oxygen when the pressure is reduced. Finally, it has beenreported that sufinates can be converted to sulfonates by reaction withoxidizing agents. In such a reaction the sulfonate produced will foam,if it is in an aqueous medium. Although the reaction of sulfinate withoxidant is not new and the art recognized the need for exothermiccosmetics, before the present invention it was not suggested to employan organic sulfinic acid' or sulfinate in a reaction with an oxidant inthe presence of cosmetic composition ingredients so as to dispense aheated cosmetic. The advantages of such a process and preparation werenot disclosed. Included among such advantages are the additions to thefinal cosmetic of a surface active agent and water, as usefulconstituents thereof, resulting from the heating reaction, with theproduction of no undesirable byproducts.

United States Patent "ice In accordance with the present invention aself-heating cosmetic, such as a pressurized foaming shaving cream, ismade by reacting and contacting with other cosmetic compositioningredients, an oxidizing agent and an organic sulfinic acid orsulfinate in a reaction which generates heat and produces a surfaceactive organic sulfonic acid or sulfonate, whereby a heated cosmetic,such as a shaving cream in foamed form, is produced, which includes as auseful constituent, surface active organic sulfonic acid or sulfonatemade by the exothermic reaction.

The invented process may be carried out by means of an container orsuitable package or a combination of containers in which there arestored separately the oxidant and reductant and which includes means forsimultaneously discharging both oxidant and reductant from theirseparate sources or compartments into contact with each other and otherconstituents. of a shaving cream or other cosmetic preparation. Thereaction heats the cosmetic while it is being dispensed. In preferredembodiments of the invention the oxidizing agent is a chemical such ashydrogen peroxide, in aqueous solution, preferably containing astabilizing agent for the peroxide, and the reductant is an alkyl-,aryl-, or alkyl aryl sulfinic acid or corresponding salt. It ispreferred to store the oxidant separately from the other cosmetic orshaving cream ingredients and it is similarly preferred to store thesulfinic acid or sulfinate reductant with the other ingredients.

Plural compartment pressurized dispensers are known and are incommercial use. Usually, a single container includes a main compartmentwhich contains liquefied gas and other ingredients, plus a smallercompartment, which is collapsible, a valve or a plurality of valvescommunicates with the contents of the compartments via dip tubes orequivalent connections so as to allow simultaneous, joint dispensing ofthe contents, when desired. The valve or valves may be actuated bydepression of a spout member, in which the contents of the compartmentsare mixed and from which they are discharged to the consumer. One suchdispenser is illustrated in US. Pat. 3,325,056, although it is preferredto employ a design wherein the mixing of the components of theexothermic cosmetic occurs externally of the container, in the spout.Another apparatus that may be utilized for producing the heated cosmeticis illustrated in US. patent application S.N. 560,299, filed June 24,,1966 by Alan Dillarstone, wherein two dispensers, each containing one oftwo materials to be dispensed together, are joined and operatedconcurrently, discharging a mixture of materials through a common spout.

As the oxidant and reductant are mixed, they react to generate heat andwarm the cosmetic in which they are incorporated. By employment ofstoichiometric proportion of reductant and oxidant optimum heat will begenerated but it is sometimes desired to speed the reaction by using anexcess of one of the reactants, usually the oxidizing agent. With aparticular cosmetic or shaving cream composition being dispensed,orifices and passageways of the valve parts may be so designed toprovide the desired proportions of reactant materials. Where it isconsidered to be useful for the consumer to have some control of thetemperature to which the cosmetic is raised by the exothermic reaction,the dispensing valves for plural compartments may be independentlyactuated, at least to an extent, so that the proportions of reactantsmay be altered, allowing more or less heat to be generated, depending onthe ratios of oxidant and reductant compositions being dispensed. Thetemperature to which the cosmetic is raised will usually be controlledby the valve design or the user so that it does not become unbearablyhot; the maximum temperature at which dispensing will usually occur isfrom F. to l60 F. and will rarely exceed 150 F. The permitted rise intemperature of the cosmetic over room temperature will usually be lessthan 10 F. and most often will be about 60 to 80 F. The heating willordinarily raise the temperature of the cosmetic at least about 30 F.and the minimum temperature at which the heated cosmetic is dispensedwill be about 100 F., although most products will be heated to at least120 F. However, it is within the scope of the present disclosure toemploy other dispensing temperatures, under appropriate circumstances.

The organic sulfinates or sulfinic acids of this invention are of theformula RSO M, wherein R is hydrocarbyl or substituted hydrocarbyl,preferably alkyl, aryl or alkyl aryl, and M is either hydrogen or asalt-forming cation. The aliphatic hydrocarbyl groups, which may containup to 26 carbon atoms and usually up to 20 carbon atoms, for bestperformance, are preferably saturated and of straight chain structure,although alkyl groups thereof may also be branched. In the compoundswherein the sulfur of the sulfinate radical is joined to an alkyl thejoining is preferably at a primary or secondary carbon atom, althoughlinkage to a tertiary carbon is also useful. For the aromatic compoundsthe sulfur is preferably joined to a benzene ring, although it may alsobe substituted onto a naphthalene or other aromatic nucleus. Thearomatic nuclei may have joined to them alkyl groups of 1 to 20 carbonatoms, preferably attached to a benzene ring either at the end or nearthe end of the alkyl chain, usually no more than three carbon atomsremoved therefrom. Such an alkyl group will preferably be located parato the sulfur of the sulfinate or sulfinic acid.

Although both aliphatic and aromatic sulfinic acids and sulfinates arewithin the scope of the present invention, the aromatic compounds arepreferred and the salts thereof are preferred to the free acids becauseof greater compatibilities with cosmetic constituents, better utilitiesof the corresponding sulfonates as components of the cosmetics, improvedstabilities and greater solubilities in the cosmetics. The alkali metaland alkanolamine salts of benzene sulfinic acid and alkyl benzenesulfinic acids are especially preferred.

-In addition to generating heat rapidly and efiiciently when reactedwith hydrogen peroxide or other suitable oxidants, the salts of benzenesulfinic acid and lower alkyl benzene sulfinic acid, such as thosecontaining 1 to 3 carbon atoms in an alkyl side chain, impart ahydrotropic elfect to the cosmetic composition upon oxidation of thesulfinate to sulfonate. Thereby, the cosmetic is improved by thehydrotrope solubilizing various constituents thereof and improvingwetting action. Alkali metal and organic salts, particularly thepotassium and ammonium salts of benzene sulfonic acid and lower alkylbenzene sulfonic acids are used widely in cosmetic and detergentproducts to aid in the production of homogeneous and fluid compositions.

n supplementing or if desired, replacing entirely the benzene sulfinateor lower alkyl benzene sulfinate with a higher alkyl benzene sulfinate,preferably of to 16 carbon atoms in the alkyl chain, the heat-generatingaction is accompanied with the production of long chain alkyl benzenesulfonates, which are known to be excellent detergents and are oftendesirable constituents of cosmetics for their detersive and surfaceactive properties. The higher alkyl sulfinates, of 10 to 16 carbon atomsmay also be used for similar purposes, since they are converted to thecorresponding alkyl sulfonate detergents.

The aromatic sulfinic acids and sulfinates may be alkylated orpolyalkylated and may contain other non-interfering or compatiblesubstituents. Among suitable substituents are lower alkoxy groups of 1to 4 carbon atoms, all the halogens, hydroxy, sulfonic, carboxy andother compatible groups. Usually, only one each substituent will beemployed and that will ordinarily be on the aryl group, but up to threesubstituents may be present and they may be the same or different.

The salt-forming cations may be any such suitable ion but willpreferably be one that is usually found in cosmetic preparations.Ammonium or alkylolamine are preferred but alkali metal and other metalsalt-forming ions may also be used. When accompanied by otherconstituents of a shaving preparation, sulfinate will usually bepresent, rather than the sulfinic acid, because of the alkalinity of thoshaving preparation. Among suitable alkylolamines that may be used aretriethanolamine, diethanolamine, ethanolamine, triisopropanolamine,isopropanolamine, diisopropanolamine, N-methyl diethanolamine,N,N-dimethylethanolamine, N-methyl ethanolamine, N-ethyldiisopropanolamine, N,N diethyl n-butanolamine, and other loweralkanolamines having from 1 to 3 alkanolamine groups of 1 to 4 carbonatoms per alkanol. The alkyls of the alkanol groups may be substitutedby non-interfering radicals, such as halogens, lower alkoxy or othersimilar substituent. Alkali metal salts are also useful sulfinates,including the sodium, potassium and lithium salts. Alkaline earth metalsalts, zinc, tin, magnesium and aluminum sulfinates may be used, whensuitable in the formula being dispensed. In short, any non-interferingmetal or other salt-forming cation may be employed to make a suitablesulfinate, as long as it possesses suflicient solubility. Bynon-interfering it is meant that it does not prevent theoxidation-reduction reaction or significantly adversely affect thechemical, physical or aesthetic properties of the cosmetic beingdispensed. In this respect, it will be noted that the preferred ammoniumand alkylolamine salts are milder to the skin than many of the metallicsalts, although where mildness is not an important consideration themetal salts can be used equally well.

The sulfinic acid reductants are stronger acids than the carboxylicacids. They form stable salts, which may crystallize with water ofhydration. The aromatic sulfinic acid compounds are usually of greaterstability than the aliphatic analogues, and the salts are more stablethan the acids. Sulfinic acids are most frequently prepared by theaction of a reducing agent, such as zinc or sodium sulfite, on asulfonyl halide, such as a chloride or a bromide, in neutral or basicaqueous or alcoholic medium. They may :also be prepared from Grignardreagents and sulfur dioxide. Of course, the products made areconvertible to either the acid or salt form by treatment with acid orbase, as the case may be. Methods of preparation which are adaptable toproduce the sulfinic acids and sulfinates of this invention aredescribed in Chemical Review, vol. 48, pages 69-124 1951) by W. E. Truceand A. M. Murphey and in the Journal of Organic Chemistry, vol. 7, pages23-30 (1942) by P. Allen, Jr.

As examples of sulfinates that may be used in accordance with thisinvention there are listed the following:

Sodium ethanesulfinate;

magnesium butanesulfinate;

sodium l-dodecanesulfinate;

potassium l-pentadecanesulfinate; triethanolamine propanesulfinate;

ammonium l-tetradecanesulfinate;

sodium benzene-sulfinate;

ethanolamine benzenesulfinate; triethanolamine paratoluenesulfinate;potassium para-toluenesulfinate;

methylamino ethanol benzenesulfinate;

methyl diethanolamine ortho-toluenesulfinate; sodiumpara-chlorobenzenesulfinate;

lithium ortho-toluenesulfinate;

potassium para-methoxybenzenesulfinate; diethanolamine para-(l-methylethyl)-benzenesulfinate; lithium meta-dodecylbenzenesulfinate;potassium paradodecylbenzenesulfinate; sodiumpara-dodecylbenzenesulfinate; triethanol aminepara-dodecylbenzenesulfinate; sodium 1-chloronaphthalene-6-sulfinate;and ethyl diisopropanolamine para-propylbenzenesulfinate;

and the corresponding free acids.

The oxidizing agent which may be reacted with the sulfinic acid orsulfinate may be any of such materials which is capable of convertingthe sulfinate to sulfonate, with the evolution of sufficient heat towarm appreciably the cosmetic being dispensed. Although various organicoxidants may be used, it is preferred to employ percompounds to convertthe sulfinates to sulfonates. F or simplicity, when sulfinate andsulfonate are recited herein the terms include the corresponding acids,too. Among the per-compounds, the inorganics are preferred, especiallythose which are converted to innocuous or helpful byproducts by theoxidation reaction. Among the most preferred is hydrogen peroxide,preferably in aqueous solution, but sodium peroxide, sodium perborate,potassium percarbonate, sodium persulfate and urea hydrogen peroxidefind use, too. Thus, alkali metal, alkaline earth metal and other metalper-compounds and compounds which provide hydrogen peroxide for thepresent reactions are oxidants contemplated as within this invention. Toobtain special properties, mixtures of the oxidants may be used.

Although many different oxidizing agents may be used to convert thesulfinate to sulfonate and generate heat to warm the cosmeticcomposition, it has been found to be most preferable to use hydrogenperoxide, preferably in a stabilized aqueous solution, as will beobserved, the by products from hydrogen peroxide are limited to water ifthe oxygen is consumed in converting the sulfinate to sulfonate. Wateris a normal constituent of cosmetic compositions and shaving creams anddoes not add irritating cations or other interfering ions to theproduct.

It is preferred to employ the oxidizing agent as a separate aqueoussolution, apart from the other cosmetic and reducing agent constituentsof the cosmetic preparations. Various concentrations of oxidant in watermay be used, usually from 3 to 30% by weight. When hydrogen peroxide isused, so as to maintain container size as small as possible and topromote efliciency in the heat-generating reaction, there should beemployed from 5 to 30%, preferably 8 to 15% and most preferably, from 9to 12% hydrogen peroxide in aqueous solution. Minor amounts ofsequestrants, chelating agents or other stabilizers, such asnitrilotriacetic acid or its trisodium salt, ethylene diaminetetraacetic acid or salt thereof, stannic chloride, silicates or otherknown compounds for stabilizing purposes may be present with thehydrogen peroxide.

The oxidizing action of the hydrogen peroxide is increased considerablyby the presence of metal catalysts. Thus, tungstates, molybdates anduranates and other salts and catalytic materials for releasing activeoxygen from the per-compound or promoting its activity may be used toincrease the reaction efiiciency of a redox system employing hydrogenperoxide as the oxidant. Usually the alkali metal or ammonium salts areused, e.g., ammonium molybdate, potassium tungstate, sodium uranate.Because metals that activate hydrogen peroxide systems might also act toconvert the hydrogen peroxide to a less stable form, in accord with thepresent invention the catalyst will usually be incorporated in the zonecontaining the sulfinate and will not contact the stabilized hydrogenperoxide until such time as the reaction between reductant and oxidantis to be effected.

The other constituents of the cosmetic compositions are those known tothe art to impart the desired cosmetic properties for the particularpurpose. Most cosmetics and shaving preparations include hydrophilic andlipophil-ic components, usually in their respective phases, togetherwith an emulsifying or wetting agent to help form a stable emulsion. Forexample, in a hand cream the lipophilic phase can include lanolin,mineral oil, stearic acid, petrolatum, animal fats, vegetable andpetroleum waxes and emollients, while the aqueous phase may containwater, glycerol, other solvents and buffers, with soaps or syntheticorganic emulsifiers to produce and maintain the emulsion.correspondingly, in hair-removing preparations,

the active depilatory may be present in either phase, although it isusually water soluble and therefore, is found in the aqueous phase, forthe most part. In some cases, instead of employing emulsions, solutionsof an ingredient may be used. Material dispensed may be in liquid,paste, gel or preferably, in foam form. The foams are created by theaction of a dissolved pressurized or liquefied gas dispersed through thecomposition, which is released as a gas and expands the composition.

In shaving preparations, the shaving emulsion dispensed from onecompartment of a pressurized container comprises a major proportion, upto about of water, and the rest of the material includes soap or otherbeard softeners, solvents, emulsifying and conditioning agents. The soapis preferably a stearic acid soap, made from commercial double or triplepressed stearic acid. However, other higher fatty acid soaps, such asthose of tallow, corn oil, cottonseed oil, animal greases and otheranimal fats and vegetable oils may be employed. Usually however, a majorproportion of the soap-forming fatty acid of the soap should be of 16 to18 carbon atoms. The cation of the soap is preferably an alkanolamine,such as triethanolamine, although other tri-, diand monoalkanolamines of1 to 4 carbon atoms per alkyl group are useful. If desired, alkali metalsoaps, such as sodium and potassium soaps may be employed, as may beammonium and lower alkyl amine soaps. For best results in producing asoap which does not irritate the skin after shaving and which is fluidenough so as to be dispensed entirely from the container atriethanolamine soap is used, together with minor proportions of sodiumand potassium soaps to stabilize the lather. Where superfatting effectsare desired, the fatty acid employed may be only partly neutralized bythe cation of neutralizing agent, leaving the free fatty acid present toexert its emollient effect upon the skin.

Alkylolamides also have a conditioning effect on the hair and skin, inaddition to stabilizing foams of cosmetic compositions. Included in thealkylolamide group are dialkylolamides, such as lauricmyristicdiethanolamide, and other alkylolamides wherein the acyl groups are of12 to 18 carbon atoms, preferably with 50% by weight or more being of 12to 14 carbon atoms. The alkylol groups are preferably of 1 0t 3 carbonatoms each.

As emollients or solvents it is preferred to employ polyhydric alcoholsof 3 to 6 carbon atoms per molecule, having 3 to 6 free hydroxyls permolecule. Exemplary of such compounds are glycerol and sorbitol,although other alcohols such as pentaerythritol, mannitol and othersugar alcohols are also used.

Various suitable emulsifying or surface active agents may be importantigredients of the present products and these include the anionic,cationic and nonionic compounds. Of these materials it is preferred touse the nonionics and of these the most preferable group is that of thehigher ethers of ethoxylated alkyl phenols and of higher fatty alcohols.These compounds, known commercially as Igepals, a trademark of GAFCorporation, usually have an alkyl group of 6 to 10 carbon atoms on thephenol ring and the degree of ethoxylation is from 1 to 50 ethoxy groupsper molecule, with the higher fatty alcohol being of 10 to 18 carbonatoms per molecule, usually averaging about 12 carbon atoms. Othernonionic compounds, such as esters of higher fatty acids and ethoxylatedalcohols, condensates of groups of higher ethylene oxide polymers andhigher propylene oxide polymers, and esters of ethoxylated fatty acidsand sugar alcohols or hexitane are representative of the nonionics thatmay be included in the present formulations. Among the anionic surfaceactive agents are the higher alkyl sulfates and alkyl sulfonates, thehigher alkyl benzene sulfonates, ethoxylated fatty alcohol sulfates,monoglyceride sulfates, higher fatty acid amides of amines, such assodium lauroyl sarcoside, phosphates corresponding to theabove-mentioned sulfates, and sulfates and sulfonates of the mentionednonionic compounds, where possible. Among the cationic surface activeagents may be mentioned the quaternary ammonium and phosphoniumcompounds, e.g., trimethyl benzyl ammonium chloride, cetyl trimethylammonium bromide and lauryl pyridinium chloride, all of which exertantiseptic, as well as surface activity.

In self-pressurized aerosol compositions a liquefied gas, such as alower hydrocarbon or a lower halogenated hydrocarbon, may be employed toaid in discharging the oxidant and reductant portions of the cosmeticpreparation. Especially when the liquefied gas is emulsified into one orboth of the portions of the cosmetic, it will assist in generating afoam as the liquefied propellant is converted to minute gas bubbles. Ifit is desired to use only water and hydrogen peroxide or other oxidanttherein, instead of liquefied hydrocarbon or liquefied halogenatedhydrocarbon, compressed nitrogen, carbon dioxide, oxygen or othernon-liquefied gas may be used, to provide the force to discharge theoxidant material. Among the liquefied gas propellants which may beemployed are the lower hydrocarbons of 3 or 4 carbon atoms, whichinclude n-butane, isobutane and propane, preferably employed as amitxure of isobutane and propane, preferably 85 to 90 parts isobutaneand 10 to 15 parts propane. The halogenated hydrocarbons are preferablythose which are at least partially fluorinated, includingmonochlorotrifluoromethane, dichlorodifluoromethane,trichlorotrifluoroethane, dichlorotetrafluoroethane,monochloropentafluoroethane, trichloromonofiuoromethane,tetrachlorodifiuoroethane, and similar chlorofluorohydrocarbons, having1 ot 3 carbon atoms per molecule. Of course, mixtures of the halogenatedhydrocarbons are also employed, desirably to regulate the pressuredeveloped, solubilizing properties, corrosion prevention, emulsionformation, and so forth. In some instances it may be desirable toutilize completely chlorinated or fluorinated hydrocarbons aspropellants or diluents, e.g., methylene chloride, where they areacceptable.

All cosmetic compositions contain adjuvant materials to make the productaesthetically acceptable or specially appealing. Perfumes, dyes,pigments, emollients, solvents, thickeners, solubilizers, humectants,buffers, antiseptics, foaming agents, preservatives and similarmaterials, generally in minor proportions, usually less than each andpreferably less than 2% each and most preferably less than 1% each, withthe total thereof being less than 25%, preferably less than and mostpreferably less than 5% of the composition, are often employed.

The proportions of various other constituents of the presentcompositions are regulated to a large extent by the type of compositionbeing prepared. Usually for cosmetic compositions there will be presentfrom 2 to 50% of the active cosmetic ingredient, although more or lessmay also be employed in special cases. There will also usually beemployed from 5 to 90% solvent or dispersion medium and from 1 to 25% ofsurface active agent, which group includes soaps. In some circumstances,as in shaving creams, the active ingredient and the surface active agentmay be the same, since one compound serves both functions. Inpressurized compositions, there with usually be present from 3 to 90% ofliquified or compressed gas. Of course, the given proportions apply tomost cosmetics, but it must be realized that for certain compositionsproportions outside the given ranges may also be acceptable, evenpreferred.

Pressurized shaving creams preferably contain from 50 to 75% water, morepreferably 55 to 65%, 1 to 20% of, synthetic organic surface activeagent, exclusive of that produced by the redox reaction, preferably 1.5to 4% thereof, or 10 to 40%, including such products, 5 to 20% soap,preferably 8 to thereof, and 2 to of humectant, such as glycerine orsorbitol, which may also exert a solvent action in the composition.Preferably, there is used from 3 to 10% of such humectant. In mostcompositions minor proportions of foaming agent and perfume, bothusually within the range of 0.1 to 5% and 8 preferably, from 0.3 to 1%are also often utilized. In heated shaving creams the soap solution willusually include from 10 to 35%, and preferably from 15 to 25% of organicsulfinate reactant, but the sulfinate may be separately dispensed, too.Together with the sulfinate or separately dispensed will often bepresent 0.2 to 2%, preferably 0.3 to 1% of molybdate or tungstatecatalyst, or other suitable catalyst for the reaction in desirableamount. The hydrogen peroxide contained in the separate compartment toavoid premature contact with the reductant will usually be from 1.5 to5% of the weight of the soap solution and will be present as an aqueoussolution of from 3 to 30% strength. Thus, the hydrogen peroxide solutioncan be from 0.4 to of the soap' solution weight and is preferably about20 to 30% thereof.

The pH of shaving preparations is normally regulated to be on thealkaline side and is preferably no higher than 10.5. Thus, it ispreferable to employ compositions having a pH of 7 to 10, although thoseof pH. from 5 to 11 may also be used, when desired for a particular typeof application. The pH may be regulated by use of compatible buffers,such as acid-base, salt-base and acid-salt mixtures, e.g., includingborates, phosphates, carbonates, sulfates or silicates, or otheracceptable inorganic or organic salts, including salts of alkylolamines.The soap or soaps present in the shaving compositions may exert abuffering effect and may be the primary or even the sole bufferspresent.

The cosmetic preparations of this invention are made by simple methodsknown to the art. The various constituents of the cosmetic portion ofthe preparations themselves may be combined in the normal manner andthen, depending on the nature of the cosmetic, may be further formulatedwith either the oxidizing agent or the reducing agent employed. If thecosmetic preparation is essentially oxidizing in nature, it willpreferably be combined with the oxidizing agent. The reverse situationis also applicable and in most cases, the cosmetic will have theingredients thereof packed together with the reductant and catalyst,with the oxidant being separately packaged, usually in a differentcompartment of the dispenser. If some of the constituents of thecosmetic are oxidizing and others are reducing by nature, thecomposition may be formulated by such parts and one part may accompanythe heat-generating oxidant and the other may be stored with thereductant. The main consideration is that no unwantedoxidation-reduction should occur due to premature combination of aheat-generating chemical of this invention with a cosmetic ingredient.Of course, if so desired, the oxidizing agent and the sulfinate may bekept separate and not formulated with any other cosmetic component. Insuch situations, the cosmetic may be separately dispensed from acontainer and only brought into contact with the heat-generatingchemicals upon discharge from the container. In such an arrangement athree-compartment container may be employed or three or other number ofseparate containers may be used in conjunction.

Self-heating cosmetic preparations of this invention include variouscompositions intended for application topically to the human body.Usually these are applied to the skin or hair. They include face creams,body lotions, depilatories, tanning agents, antiperspirants,sun-screens, personal deodorants, hair creams, hair lotions, hair gels,shampoos, dyes, bleaches, rinses, shaving creams makeup preparations,bath oils, facial treatments, astringents, after-shave lotions and manyother related preparations. In most of these, organic sulfonatedetergents, hydrotropes or other surface active agents are important oruseful constituents, either as detergents, hydrotropes, emulsifiers oras contributors of desirable wetting or surface active properties. Bythe method of the present invention, such compounds are prepared in thedispensing of the cosmetic during the heating thereof and areimmediately solubilized or dispersed in the cosmetic, partly due to theheat generated in the exothermic reaction which produced them. The heatgenerated produces small currents in the cosmetic being dispensed whichhelp to distribute the surface active sulfonate and by distributing thesulfonate throughout the composition, the ease of wetting the variousareas of the cosmetic preparation is further increased. The heatgenerated also helps further to solubilize cosmetic preparationingredients and thereby improves homogeneity of the product. Thiscoaction between the surface active agent produced, the heat generatedand the other cosmetic preparation ingredients is a useful result of thepresent invention and helps to avoid poorly dispersed ingredients orproducts of the exothermic reaction. The surface activity of thesulfonate made also helps to distribute throughout the cosmetic thewater and other byproducts of the heating reaction and thereby effects abetter and more even heating of the cosmetic. Thus, pockets ofundispersed materials in the cosmetic are avoided and final product isuniform.

Among other advantages of the present invention are the reasonable costsof the oxidants and reductants and their low corrosivity toward ordinarymaterials of container construction, such as tinplate or steel coatedwith resins commonly used for that purpose. Thus, blockages of valveparts are not encountered, due to corrosion byproducts being releasedinto the cosmetic being dis pensed through the valve. In addition to lowcorrosive action, the present oxidants and reductants are remarkablycompatible with normal cosmetic ingredients and do not form undesirableproducts that would adversely affect the cosmetic properties of thepreparations. It is considered to be important in most cases that theproducts of the exothermic reaction are not gaseous, since the presentsystems are thereby made useful for liquids, emulsions and creams, aswell as foams. Of course, by use of propellants, such as liquefiedgases, emulsions may be dispensed as foams and liquids may be dispensedas sprays, when desired. Here again, it is important that the presentexothermic compositions not change the foaming activity of the liquefiedgases or other foaming agents, so that the foaming obtained can bepre-planned, being dependent on the ingredients of the composition used,without being affected by additional gases produced in the heatingreactions. Thus, except for the expansion of the foam on heating, theregular tried and tested proportions of foaming agents or sprayingagents may be used with the cosmetics. Of course, the heat expansiondoes increase foam volume and can help save propellant, to some extent.

The lack of gas production in this reaction is a protective feature ofthe invention because accidental rupturing of a sac containing areactant will not result in gas generation. If it did, the pressurecreated could cause the container to explode. It has been found that thepresent exothermic reaction, even if initiated by sac leakage, will notcause such explosion.

Although all the above-mentioned properties are of importance inproducing a satisfactory self-heated cosmetic, a most important propertyis low toxicity of the heat-generating chemicals. The present materialsare low in toxicity and are completely suitable as ingredients incosmetics. They are converted into sulfonated compounds which arewell-known constituents of materials that have positions within thepresent invention. Of course, such examples are not to be considered aslimiting the invention, because they are only exemplary thereof. Thoseof skill in the art will know how to replace various constituents andprocedural steps of the invention with corresponding equivalentmaterials or operations without departing from the principles orteachings imparted herein. Unless otherwise stated, all parts given byweight.

EXAMPLE 1 Parts (by Weight) Stearic acid (double pressed) 8 0 Thestearic acid, sorbitol and nonionic surface active agent are mixedtogether and heated to 185 F. The triethanolamine and water are combinedand heated to the same temperature, and then both of the portions arecombined at 185 F. Next, the sodium hydroxide is added, with mixing. Theemulsion resulting is cooled to F. and the perfume, triethanolaminetoluene sulfinate and ammonium molybdate are added, with mixing, afterwhich the resulting perfumed emulsion is further cooled to 80 F. Thisportion of the cosmetic preparation, including all the cosmeticingredients plus the reductant and catalyst for the redox reaction, isthen added to the larger compartment of a plural compartment dispensingcontainer. Then, 25 parts of an 11% aqueous solution of hydrogenperoxide, containing about 0.2% of phenacetin as a stabilizer, arefilled into the smaller compartment or sac of the dispenser. Bothcompartments communicate with a dispensing valve or valves. Thedispensing valve is then staked into place at the outlet of thedispensing container. 6.0 parts of propellant, in the gaseous state, arethen pressure filled into the larger compartment, from which propellantpressure is exerted on the materials in both compartments. Thehydrocarbon propellant is a mixture of 83.5% isobutane and 16.5%propane. The pressurized shaving cream is now ready for use.

The pressurized product made by the method of this example has anexcellent shelf life. When the dispensing valve of its container isactuated the shaving cream dispensing is an effective softener for thebeard and permits almost effortless, smooth and pleasant shaving. Inpart, this result is attributable to the temperature of the shavingcream dispensed, which rises to about 140 F. within thirty seconds afterdispensing it with the oxidant and reductant from the container, at 70F. The cream is pleasantly perfumed and there is no malodorous componentevident.

Comparable results are obtained when the triethanolamine sulfinate oftoluene is replaced by triethanolamine benzene sulfinate ortriethanolamine xylene sulfinate or a mixture thereof. To obtainadditional detersive and Wetting action, triethanolamine dodecyl benzenesulfinate may be substituted for the other sulfinates, either in wholeor in part, and a sumilarly effective product results. When the amountof peroxide is decreased to 13 parts, less heating is obtained and thetemperature of the cream reaches only about F. thirty seconds afterdispensing.

When 4.5 parts of triethanolamine are employed instead of the 4.0 partsof the formula given above, and no sodium hydroxide is used, with theomitted /2 part made up by additions of A2 part water to the formula, agood self-heating shaving cream results with essentially the sameproperties as those described above. However, the

lather is more fluid and is not as firm or stable as that of the formulaincorporating the small proportion of sodium soap. Similarly, when thesodium hydroxide is replaced with potassium hydroxide in stoichiometricproportion a firmer lather results than that from the triethanolaminesoap alone. Reducing the hydrogen peroxide concentration to does notsignificantly adversely affect either the temperature to which thelather is raised or the speed of heat generation.

When ammonium molybdate is replaced with alkali metal tungstate ormolybdate, in these essentially triethanolamine soap formulas, catalyticaction falls off. Apparently, it is desirable to have the cation of thecatalyst the same as that of soap and sulfinate, or at least to All aregood self-heating shave creams, being at a temperature of about 130 to150 F. one minute after dispensing. The lather is not as thick as thatof the product of Example 1.

When the proportion of propellant is changed so that from 3 to 10% byWeight thereof is present, efficient dispensing is encountered over therange, with faster dispensing and greater foaming being obtained at thehigher propellant ratios, as would be expected.

In similar experiments, wherein cetyl alcohol, glycerine or otherhumectants and emollients are added to the compositions made, littledifferences in heating properties or stabilities are found. When theratios of catalyst are halved or doubled, heating times are affectedsomewhat.

have it contain nitrogen, as in ammonium, if the soap and When excessperoxide, from 0.1 to or of the sulfinate contain nitrogen.stoichiometric amount is used, the reaction is hastened EXAMPLES 2-9Parts by weight Stearic acid (triple pressed) 6.3 6.3 4.0 5.6 4.0 6.34.0 6.3 Clo-O16 fatty acids (from coconut oil) 2.7 2.7 2.7 2.4 2.7 2.72.7 2.7 Light mineral oil 10.0 10.0 Triethanolamine 4.6 4.6 3.0 17.412.0 4.6 3.0 4.6 Sorbitol (70% aqueous solution) 10.0 10.0 10.0 8.9 10.010.0 10.0 10.0 Water 75.9 75.9 69.8 67.5 41.5 65.9 69.8 65.9 Perfume 5.00.5 0.5 0.5 0.5 0.5 0.5 0.5 Lanolin esters (Amerchol 101) 10.0 10.0Potassium benzene snlfinate(45% aqueous solution).- 37.5 37.5 37.5 26.537.5 Sodium tungstate (10% aq. solution) 4.2 4.2 4.2 3.0 4.2 3.6 3.9Hydrogen peroxide (11% aq. solution) 35.0 35.0 35.0 25.0 35.0 30.0 32.7Propellant (5:1 mixture of isobutane and propan 5.4 5.4 5.5 3.8 5.4 4.75.0 Triethanolamine toluene sulfinate (92.3% active) 17.5 17.5 28. 2

Self-heating facial cleaner compositions of the formula but even withonly the stoichiometric amount, it proceeds given above in Examples 2-9are made, following the quickly and the shaving cream is ready for usesoon. general method of Example 1, modified for the present When thebase formula is replaced by a conventional compositions by adding thecoconut oil fatty acids and foaming anionic shampoo, a foamable hairconditioner, mineral oil or lanolin esters with the stearic acid and ora sun-screening cosmetic containing foaming agent, heating to 185 F.,and then proceeding to prepare and the corresponding self-heatingfoaming product is disfill the dispensers. All of the products areheated foampensed correspondingly. When non-foaming materials ingcleanser cosmetics, with the temperatures to which such as facialemulsion, skin cream, or deodorant forthey are raised being from 120 F.to 150 F. As is seen mulations, which may contain anti-foaming agents,are from the formulas, some are superfatted and some consubstituted forthe base formula, non-foaming but surface tain excess triethanolamine.active heated products are made.

EXAMPLES 1012 EXAMPLES 13-15 Parts Parts Water 54.9 Water 46.6 Stearicacid 7.7 Stearic acid 7.7 Coconut oil fatty acids 1.0 Coconut oil fattyacids 1.0 Lauric myristic diethanolamide 1.0 Laurie myristicdiethanolamide 0.5 Triethanolamine 4.8 Cetyl alcohol 0.5 Perfume .75Triethanolamine 10.0 To the above base formulation are added thefollowing gq hydroxlde (342% 50m) to make the products of Examples10-12, respectively: er mm 1 To the above formulation are added the folowing to EXAMPLE 10 Parts make the products of Examples 13-15. Baseformula 99.6 EXAMPLE 13 Triethanolamine toluene sulfinate (92.3% Partsactive) 31.0 Base formula 99.0 Sodium tungstate dihydrate (11.3% aq.soln.) 4.4 Potassium benzene sulfinate (45.4% aq. soln.) 41.6 EXAMPLE 11Sodium tungstate (10% aq. soln.) 4.4

p Parts EXAMPLE 14 Base formula 105.5 Parts Potassium toluene sulfinate(49.4% active) 38.0 Base formula 104.4 Sodium tungstate (10.0% activeaq. soln.) 1.5 Trietlllilanolamine toluene sulfinate (76.3% aq. 6

so 3 .3 EXAMPLE 12 Parts Sodium tungstate 10% aq. soln.) 4.4 Baseformula 99.0 EXAMPLE 15 Potassium benzene sulfinate (45.4% active aq.Parts 13 41.6 Base formula 105.5 Sodium tungstate (10% active aq. soln.)4.4 Potassium toluene sulfinate (49.4% aq. soln.) 38.0 The boveformulations are prepared as in Example 1 Sodmm tungstate (10% soln) andare filled into dispensing containers with 36 parts of The aboveformulations are prepared in the manner an 11% aqueous hydrogen peroxidesolution in a separate described for Examples 10-12 and are filled intodual zone and with 5.5 parts of the propellant of Example 1. compartmentdispensing containers with six parts of the propellant of Example 1 and36 parts of 11% aqueous hydrogen peroxide. The products dispensed aregood shaving creams, with that of Example 14 being rated milder to theface. The cream of Example 13 is thicker than that of Example 15. Allheat to 120 to 150 F. in to 60 seconds.

When other active ingredients are added to those formulas, such as dyes,skin conditioners, bactericides, fungicides, compatible bleaches, etc.,the products are uesful in performing the cosmetic functions of suchadditives.

What is claimed is:

1. A self-heating cosmetic product comprising constituents stored inseparate zones of a container or containers in one of which zones thereis present from about 10-35 percent by weight of an organic sulfinicacid or sulfinate reductant of the formula RSO M, wherein R is anunsubstituted or substituted hydrocarbyl selected from the groupconsisting of alkyl of 10 to 16 carbon atoms, phenyl, lower alkylphenylwherein the lower alkyl is of 1 to 3 carbon atoms, and higheralkylphenyl in which the higher alkyl is of 10 to 16 carbon atoms, thesubstituents being selected from the group consisting of lower alkoxiescarboxyl, with from 1 to 3 thereof being present, and M is hydrogen or asalt-forming cation selected from the group consisting of ammonium,lower alkanolamine of 1 to 3 alkanol groups and 1 to 4 carbon atoms peralkanol group, alkali metals, alkaline earth metals, zinc, tin,magnesium and aluminum, and in another of which zones there is presentat least about the stoichiometric amount of an oxidizing agent forreaction with said reductant, said oxidizing agent being selected fromthe group consisting of hydrogen peroxide, urea hydrogen peroxide,alkali metal peroxide, alkali metal perborate, alkali metalpercarbonate, alkali metal persulfate, alkaline earth metal peroxide,alkaline earth metal perborate, alkaline earth metal percarbonate andalkaline earth metal persulfate, said oxidizing agent beingexothermically reactive with the reductant to convert it to a surfaceactive organic sulfonic acid or sulfonate and simultaneously to heat theproduct when dispensed, and from about 390 percent by weight of apressurized gas in at least one of the zones and means for dispensingcontents from both zones simultaneously and into contact with eachother, whereby there is produced by exothermic reaction of the sulfinicacid or sulfinate and the oxidizing agent a heated cosmetic preparationincluding therein the organic sulfonic acid or sulfonate produced, as asurface active constituent thereof.

2. A product according to claim 1 wherein the reductant is an alkalimetal phenyl sulfinate or alkali metal alkylphenyl sulfinate wherein thealkyl is of 1 to 3 or 10 to 16 carbon atoms, and the oxidizing agent isaqueous hydrogen peroxide.

3. The product of claim 1 wherein said product additionally containsfrom about 250 percent by weight of a soap selected from the groupconsisting of lower alkanolamine, ammonium, and alkali metal soaps offatty acids in which a major proportion of the fatty acid content is of16-18 carbon atoms and wherein said alkanolamine has from 1-4 carbonatoms per alkyl group.

4. A product according to claim 3 wherein the cosmetic is a cleansercomposition.

5. A self-heating aqueous shaving cream product comprising constituentsstored in separate zones of a container in one of which zones there ispresent from about 10-35 percent by weight of an organic sulfinic acidor sulfinate reductant of the formula RSO M, wherein R is anunsubstituted or substituted hydrocarbyl selected from the groupconsisting of alkyl of 10 to 16 carbon atoms, phenyl, lower alkylphenylwherein the lower alkyl is of 1 to 3 carbon atoms, and higheralkylphenyl in which the higher alkyl is of 10 to 16 carbon atoms, thesubstituents being selected from the group consisting of lower alkoxiesof 1 to 4 carbon atoms, halogens, hydroxy, sulfonic, and carboxy, withfrom 1 to 3 thereof being present, and M is hydrogen or a salt-formingcation selected from the group consisting of ammonium, loweralkanolamine of l to 3 alkanol groups and l to 4 carbon atoms peralkanol group, alkali metals, alkaline earth metals, zinc, tin,magnesium and aluminum, and in another of which zones there is presentat least about the stoichiometric amount of an oxidizing agent forreaction with said reductant, said oxidizing agent being selected fromthe group consisting hydrogen peroxide, urea hydrogen peroxide, alkalimetal peroxide, alkali metal perborate, alkali metal percarbonate,alkali metal persulfate, alkaline earth metal peroxide, alkaline earthmetal perborate, alkaline earth metal percarbonate and alkaline earthmetal persulfate, said oxidizing agent being exothermically reactivewith the reductant to convert it to a surface active organic sulfonicacid or sulfonate and simultaneously to heat the shaving cream whendispensed, and from about 3-90 percent by weight of a pressurized gas inat least one of the zones and valve means for dispensing contents fromboth zones, with the aid of the pressure of the pressurized gas,simultaneously and into contact with each other, whereby there isproduced by the exothermic reaction of the sulfinic acid or sulfinateand the oxidizing agent a heated cosmetic preparation including thereinthe organic sulfonic acid or sulfonate produced, as a surface activeconstituent thereof.

6. The product of claim 5 wherein said product additionally containsfrom about 2-50 percent by weight of a soap selected from the groupconsisting of lower alkanolamine, ammonium, and alkali metal soaps offatty acids in which a major proportion of the fatty acid content is of16-18 carbon atoms and wherein said alkanolamine has from 1-4 carbonatoms per alkyl group.

7. A shaving cream product according to claim 6 wherein the oxidizingagent is aqueous hydrogen peroxide, and the product, before dispensing,is in two separate compartments of a valved dispensing container, and asolution comprising said sulfinic acid or sulfinate, said higher fattyacid soap and water are in one compartment and said oxidizing agent isin the other, said solution including 10 to 35% of the sulfinic acid orsulfinate, the hydrogen peroxide being 1.5 to 5% of the weight of saidsolution, and the final product, after dispensing, comprising 5 to 20%soap and 50 to 75% water and being at a pH of 5 to 11.

8. A shaving cream according to claim 5 wherein the reductant is analkali metal phenyl sulfinate or alkali metal alkylphenyl sulfinatewherein the alkyl is of 1 to 3 or 10 to 16 carbon atoms, and theoxidizing agent is aqueous hydrogen peroxide.

9. A shaving cream according to claim 8 wherein there is present withthe reductant a catalyst for the redox reaction, selected from the groupconsisting of alkali metal and ammonium tungstates, molybdates, anduranates, in an effective amount to accelerate the exothermic reactionand to heat the cosmetic product to a temperature of 100 F. or morewithin 30 seconds after dispensing.

10. A shaving cream product according to claim 7 wherein the reductantis an organic sulfinate, the soap solution contains from 0.2 to 2% of analkali metal or ammonium molybdate, tungstate or uranate catalyst forthe redox reaction, the soap of the soap solution is a mixture oftriethanolamine soap and alkali metal soap with the triethanolamine soapbeing over 50% of the soap content and the pressurized gas is a mixtureof lower hydrocarbons of 3 to 4 carbon atoms or lower halogenatedhydrocarbons of 1 to 3 carbon atoms, with the halogens being selectedfrom the group consisting of chlorine and fluorine, and the proportionof such pressurized gas in the product is from 3 to 11. A shaving creamproduct according to claim 10 wherein the organic sulfinate istriethanolamine toluene sulfinate.

12. A shaving cream product according to claim 10 wherein the organicsulfinate is potassium benzene sulfinate.

13. A shaving cream product according to claim 10 wherein the soapsolution contains from 2 to of a humectant selected from the groupconsisting of glycerine and sorbitol, 1 to 20% of alkyl phenylpolyoxyethylene ethanol, wherein the alkyl group is of 6 to 10 carbonatoms and the ethoxy content is from 1 to ethoxies per mole, the productpH is from 7 to 10.5, the catalyst is present in sufiicient quantity toaccelerate the exothermic reaction so that the temperature of thedispensed shaving cream israised to at least 120 F. in 30 seconds, andthe propellant is a mixture of to parts of isobutane and 10 to 15 partsof propane.

14. A shaving cream product according to claim 13 wherein there arepresent about 20 parts of triethanolamine toluene sulfinate, 2.8 partsof hydrogen peroxide, 12 parts of mixed triethanolamine and sodium soapsof stearic acid, 5 parts sorbitol, 4 parts of nonyl phenylpolyoxyethylene ethanol, A part of ammonium molybdate, 5

16' parts isobutane and 1 part propane, together with about 58 partswater.

References Cited UNITED STATES PATENTS 6/1967 Hayes 252-90 9/1967 Moseset a1. 42447 OTHER REFERENCES 15 WILLIAM E. SCHULZ, Primary ExaminerU.S. Cl. X.R.

